Light-sensitive photographic material with antistatic layer

ABSTRACT

A light-sensitive photographic material comprising a support having coated thereon at least one silver halide emulsion layer containing (A) AN ANIONIC POLYMER HAVING A CARBOXYL GROUP OR AN ALKALI METAL SALT THEREOF AS A SIDE CHAIN THEREOF, AND (B) AT LEAST ONE OF A CATIONIC SURFACE ACTIVE AGENT AND A BETAINE-TYPE AMPHOTERIC SURFACE ACTIVE AGENT IS DISCLOSED.

United States Paten [191 Endou et a1.

[ LIGHT-SENSITIVE PHOTOGRAPI-IIC MATERIAL WITH ANTISTATIC LAYER [75] Inventors: Koutarou Endou; Masakazu Yoneyama; Nobuo Yamamoto;

Motohiro Ujihara; Yosuke Nakajima, all of Kanagawa, Japan [73] Assignee: Fugi Photo Film Co., Ltd.,

Kanagawa, Japan 221 Filed: Sept. 3, 1971 21 App1.No.: 177,815

[30] Foreign Application Priority Data Sept. 4, 1970 Japan 45-77644 52 US. Cl 96/67,96/68, 96/84 R,

[56] I -.References Cited UNITED STATES PATENTS 3,201,251 8/1965 Nadeau et a1......'. 96/87 A 1 May 21, 1974 2,882,157 4/1959 Thompson et a1. 96/87 A 3,630,740 12/1971 Joseph et a1. 96/87 A 3,547,643 12/1970 Pechmann 96/87 A FOREIGN PATENTS OR APPLICATIONS 815,662 7/1959 Great Britain 96/87 A 1,474,267 2/1967 France 96/87 A Primary ExaminerRonald H. Smith Attorney, Agent, or Firm-Richard C. Sughrue; Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A light-sensitive photographic material comprising a support having coated thereon at least one silver halide emulsion layer containing (a) an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof, and

(b) at least one of a cationic surface active agent and a betaine-type amphoteric surface active agent is disclosed.

13 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive photographic material, and more particularly to a lightsensitive silver halide photographic material having a good antistatic property.

2. Description of the Prior Art A light-sensitive photographic material is generally prepared bycoatingone' or more silver halide emulsion layers and/or subsidiary layers on an electroinsulating support, for example, .cellulose'acetate or polyethylene terephthalate. The silver halide emulsion has also an electroinsulating property. Therefore, in case of preparing and using the photographic material, an electric charge is often accumulated on the material when the surfaces thereof contact each other. The thus accumulated electrostatic charge exposes the photographic material, even if it is not imagewise exposed, and causes comet like spots on development, which are socalled static marks. The static marks result in some damage to the photographic material which isnot, in many cases, used as a'commercially available product. Since this phenomenon cannot be seen until the material is developed, it-is a very troublesome problem. Further, electrostatic charges accumulated on a support or material cause'the adhesion of dust to the surface of the material, and therefore the silver halide emulsion layer is not uniformlycoated on'the support or on a layer on the support. Saidelectrostatic charges are really generated, for example,byfriction between the film and the rollers, and by friction between the machine parts and the filmduringthe step ofwinding and rewinding films. In finished films, electrostatic charges are also generated by friction between the machine parts and the film in changing the winding of film, especially in case of movie film, and by contact with or separation from the machine parts and/or fluorescence-sensitized paper during automatic photographing of X-ray film. In addition, contact with packing materials generates electrostatic charges.

Themechanism of the electrification by friction and separation is considered to depend on the ionic state'of molecules of the material in contact. But it is difficult to forecast from structural chemistry'what material is electrified positively or negatively at present. But it is easily considered that said electrification can be prevented if the electric conductivity of the materialsurface can be increased and the electrostatic charges can be scattered in an extremely short time. Therefore, some ways to increase electric conductivity of supports of light-sensitive materials and coating surface layers of many kinds have been devised. It has been tried to use many kindsof moistureabsorbingmaterials and watersoluble inorganic salts; But there were few ways which satisfactorily prevented electrification. On the contrary, they adversely influence the photographic characteristics. Recently, however, high molecular weight materials and synthetic surface active agents have been studied for use as antistatic agents, and applications of effective materials are described in some patents.

According to these patents, most of the antistatic agents show peculiarity due to the difference of composition of the photographic coating solution,therefore,

said antistatic agent brings forth favorable results in case of particular phptographic emulsions and gelatin compositions, but in other compositions, said antistatic agents are not only useless for preventing electrification, but also do damage to the photographic characteristics. As the range of application of an antistatic agent is often limited as above, applications of many antistatic agents of different types for photography are proposed.

An object of the present invention is to provide a light-sensitive photographic material having a good antistatic property without giving rise to any harmful influence to the photographic characteristics.

SUMMARY or THE INVENTION After much research on antistatic agents, the present inventors have found that the above object can be attained by incorporating (a) an anionic polymer having a carboxyl group or an alkali metal salt thereof, and (b) at least one of a cationic surface active agent and an amphoteric surface active agent into one or more coating layers. If the anionic polymer in the present invention is used singly as an antistatic agent, the effect is very weak as will be shown in the examples hereinafter. If the amount of the addition of said anionic polymer is increased,-little improvement is obtained, which is, however, not satisfactory for practical use. On the other hand, the cationic or amphoteric surface active agent in the present invention, when used singly, gives not only small results but causes fog. The formation of fog is remarkable when the cationic surface active agent is used singly. When the anionic polymer and the cationic surface active agentor amphoteric surface active agent, each of which gives only a small effect in antistaticity, are incorporated into or coated on one or more coating layers, better results in antistatic property of photographic material are surprisingly obtained without being accompanied by adverse influences to other photographic properties.

DESCRIPTION OF THE INVENTION As an anionic polymer having a carboxyl group or an alkali metal salt thereof used in the present invention, the following are used: polyacrylic I acid, polymethacrylic acid, maleic anhydride-isobutylene copolymer, and maleic anhydride-vinyl butyl ether copolymer or an alkali metal salt thereof. And as for the cationic and amphoteric surface active agents, the following are effective: N-octadecyl-N,N,N-trimethyl ammonium chloride, N-octadecyl-N,N,N-tris-(2-hydroxyethyl)ammonium chloride, 3-tetradecyloxy-Z-hydroxy propyl pyridinium chloride, N-dodecyl-N,N-dimethyl-acarboxylic acid betaine, and the like. The cationic surface active agent and/or amphoteric surface active agent may be used with the anionic polymer.

In preparing the silver halide light-sensitive photographic material of the present invention, the anionic polymer and one of the cationic and amphoteric surface active agents in combination are incorporated into a photographic coating composition or coating layer.

In this case, the anionic polymer, and the cationic surface active agent and/or the amphoteric surface active agent may be dissolved individually in a solvent such as water or methyl alcohol and mixed with each other. The solvent may be one used in the photographic art. The two or more ingredients may be mixed simultaneously in the solvent. The solution is added to the pho- The weight ratio of the cationic surface active agent and/or the amphoteric surface active agent to the anionic polymer is not particularly limited, but is generally in the range of l/ 100 to l/l, and preferably 1/20 to H2. If the ratio of the cationic surface active agent or amphoteric surface active agent is too high, the mixture composition produces a white cloud in an aqueous solution.

The complex composition of the anionic polymer and cationic surface active agent and/or amphoteric surface active agent used in the present invention may be applied to a coating layer, for example, a silver halide emulsion layer or a subsidiary layer, such as an antihalation layer, an intermediate layer or a protective or overcoat layer simultaneously or separately. Especially, when these are added to a surface layer, more effective results can be obtained.

Further, it has been known that the antistatic composition used in the present invention is excellent as a wetting agent which is important in high speed coating, In general, high molecular weight materials of the polyanionic type have little surface active action and weak characteristics as a wetting agent. As is stated above, the cationic surface active agent is apt to increase fog. According to the present invention, it was confirmed that fog is not generated when the cationic surface active agent is used with the anionic polymer. The antistatic composition used in the present invention is added at a ratio of 0.05 g 100 g, preferably 0.1 g 2.0 g per 1 kg of a silver halide emulsion or gelatin coating composition.

As another aspect of the present invention, a processed light-sensitive photographic material may be dipped in an aqueous solution of the antistatic composition. In this case, the concentration of the aqueous solution should be in the range of 0.01 1.0 wt. percent.

The light-sensitive emulsion used in the present in vention is prepared by dispersing a silver halide, such as silver chloride, silver bromide, silver iodide, silver bromochloride, silver iodobromide or silver chloroiodobromide, into an aqueous solution of a natural or synthetic high molecular weight material, as a protective colloid, such as gelatin, casein, polyvinyl alcohol, or polyacrylic acid. Of course, the high molecular weight material may be used in combination. The coating layer may contain a water-insoluble vinyl polymer.

The light-sensitive photographic material of the present invention is used for black and white, which may include electronic recording material or for color. And the use of the light-sensitive materials are not restricted specifically.

Representative compounds among the polymers having a side chain of a carboxyl group or an alkali metal salt thereof, and among the cationic and amphoteric surface active agents are shown in the following.

Polymers having aside chain of a carboxyl group or an alkali metal salt thereof:

atoms Crim oundL' ism- L ONHCHiCOOH CompoundM Sodium alginate Cationic surface actWeEgEnE v CH,CH:OH

i8 3TN-' H2 H$0H CHzCHr 0H C1- N-octadecyl-N, N, N-tris(2-hydroxyethyl) ammonium chloride Compound 2 .CHrCHzOH Crflar-N-CHqCH, OH

HgCHz OH Br- N-octadecyl-N, N, l l-trisfl-hydrox yethybammonium bromide Compound 3 I CmCH; OH C HnN-CH1CI-Ir0li I Q momon oi- N-tetradecyl-N, N, N-tris(2-hydroxyethyl)ammonium chloride Compound 4 I CH: is ir-l F- a tin. or-

N-oetadecyl-N, N, N-trlmethylammonium chloride demand 5 C H -NCl-Ia din Cl- N-tetradecyl-N, N-dimethyl-N-benzyl ammonium chloride Compound 6 CH3 o rruocm oncmr swm H CH; B r" 8-dodecyloxy-2-hydroxypropyl-trimethylammonium bromide Compound 7 CHzCHr OH QMQoomgmmir-cmomon H HrCHrOH C1- 3-p-nonylphenyl-z-hydroxyprofilyhtisfi-hydroxyethyDammonium c o e [QaHnOCHaZHCHa-I H T- 3-tetradecyloxy-(2-hydroxypropyl)pyfldinium chloride Compound 8 cabana 9 CompoundlO C HIIC H2O H C14H -N+'-CH C 0 0 H C H2O H N-tetradecyl-N, N-(Z-hydroxjothyD-d-carboxylic acid botaine Compound 11 I k I g i 0 H2 0 H2O H C macro QHrCHCHz-NCH2C o o- H H2O H20 H N-ivetradecyloxy-(Z-hydroxypropyD-N, N -di-(2-hydroxymethyl)-acarboxylic acid betaine Compound 12 /N+CH1 CHrCHzCH CHzCOO- Modecyl-N-(Z-hydroxyethylfimidazolium-q-carboxylio acid betaine Compound 13 C H150 CH:N+'CH CO O- N-dodecyloxymethyl-N, N-diethyl-wcarboxylic acid betaine Compound 14 C H: C H2 0 )pH 0 uHmIH-(CHzCHzO )qH GHrC 0 O- N-tetradecyl-N, N-di-(polyoxyethylene)-a-carboxy1ic acid betaino (where p lq 5) Compound 15 (I) Ha C HuC ON H(CH2) a-Nf-CH:

H10 00' N-3-dodeoylaminopropyl-N, N-dimethyl-a-carboxylic acid betaine EXAMPLE 1 .A high speed light-sensitive photographic emulsion for X-ray photography containing 6 percent gelatin and 6 percent silver iodobromide, and aqueous solution of gelatin containing no antistatic agent as a surface protection layer, were applied-in succession to a cellulose triacetate support which was previously undercoated. The obtained light-sensitive photographic material was dipped in the aqueous solution of an antistatic agent of the present invention processed as the following, or in aqueous solution of a control antistatic agent.

(Preparation of the Antistatic Agent) 1 percent aqueous solution of a polymer having a side chain of a carboxyl group (Solution A). 1 percent aqueous solution of cationic surface active agent and- /or amphoteric surface active agent (Solution B). By mixing with stirring, Solution B is gradually added to Solution A until the ratio of Solution A Solution B becomes 2:] to 10:1. The obtained mixed solution is a transparent solution or turbid dispersion. preferably a transparent solution. The solution is a complex composition of an anionic polymer and a cationic surface active agent and/or an amphoteric surface active agent, which is nothing other than the antistatic agent of the present invention.

After drying, their relative humidity being adjusted to 40 percent RH, samples of a photographic film treated individually by a soaking process were led into a Faraday Gauge, passing between two rollers. And their electric charge was measured by a vacuum voltmeter. On the other hand, a white rubber sheet was put on the surface of said photographic film sample. After being subjected to regular friction by rolling on the white rubber sheet at the condition of 23C and 40 percent RH, the white rubber sheet was removed, and the obtained film was developed in a developer having the following composition at 23C, for 4 minutes. The degree of antistaticity was estimated by the quantity of built-up static marks.

or only a slight degree of antistaticity. The antistatic agent of the present invention, that is, the mixed complex composition of the anionic polymer and the cationic surface active agent or the amphoteric surface ac- 5 tive agent, however, shows a surprisingly high degree of Warm Water (50C) 700 ml i NMehYLWaminoPhenYl Sumac 4 g antiitattcity. There also no appearance of static Sodium Sulfurous Anhydride 60 g mar gygf g I h d 10 g The quantity of electric charge generated on the surgg g ggmfi y me) 5 face of the sampledeviates greatly to the negative s de Adding Water. men quantity i I 10 from the positive side where gelatin lies in the electrifi- W h w 7 n ,7 g cation serles (many of usual surface active agents are The results obtained are shown in Table 1. charged P yl TABLE 1 Concentration of Quantity of Aqueous Solution Static Electric Charge Compound (wt. Marks (V) Compound A shown above 0.2 D 2 Compound 8 shown above 0.2 C l0 Compound 1 shown above 0.2 E 14 Compound 4 shown above 0.2 E Compound 9 shown above 0.2 E 10 Compound 10 shown above 0.2 E 8 Antistatic Agent l 0.2 A 38 Antistatic Agent l 0.l A Antistatic Agent ll 0.2 A 32 Antistatic Agent ll 0.] A 26 Antistatic Agent III 0.2 A l6 Antistatic Agent Ill 0.] B -l5 Antistatic Agent IV 0.2 A 23 Saponin 0 2 D 12 No Antistatic Agent E 16 Antistatic Agent l: complex composition. prepared by mixing anionic polymer (Compound A shown above) and cationic surface active agent (Compound 1 shown above). the ratio being 5 ll Antistatic Agent ll: complex composition. prepared by mixing anionic polymer (Compound 8 shown above) and cationic surface active agent (Compound 4 shown above), the ratio being 10 Antistatic Agent lll: complex composition. prepared by mixing anionic polymer (Compound B shown above) and amphoteric surface active agent (Compound 9 shown above). the ratio being Antistatic Agent IV: complex composition. prepared by mixing anionic pol mcr (Compound B shown above). cationic surface active agent (Compound 4 shown above) an amphoteric surface active agent (Compound 9 shown above). the ratio being respectively 5 l 2.

' The estimate of the degree of antistaticity is graded into 5 steps as follows:

no appearance or static riiarks appearance of some static marks appearance of considerable static marks appearance of conspicuous static marks appearance of static marks all over the film As is evident from Table l, the respective solutions 55 of the anionic polymer, the cationic surface active agent and the amphoteric surface active agent has no EXAMPLE 2 When the mixing ratio of the anionic polymer (Compound A shown above) and the cationic surface active agent (Compound 4 shown above) was varied, the state of the solution, the degree of antistaticity and the photographic properties of the mixed complex composition were determined. The degree of antistaticity at various concentrations of the dipping process solution were also determined.

The results are shown in Table 2 and Table 3.

TABLE 2 The degree of Antistaticity at Various Mixing Ratios 9 NOTE: The concentration of the dipping process solution was 0.2%.

The methodof estimating the degree of antistaticity was the same as used in Example 1.

Where the ratio of the anionic polymer to the cationic surface active agent is more than 2/1, the solution of the mixed complex composition is transparent and the photograph is also good.

The degree of antistaticity was determined with good results when the mixing ratio is more than 3/1.

i TABLE 3 The Degree of Antistaticity of Various Concentrations of the Dipping Process Solution Anionic Polymer: Cationic Surface Active Agent 0.002% 0.0 l 0.04% 0.2%

EMS- u none:

wwww

- in Example 1.

NOTE: The method of estimating the degree of antistaticity is the same as in Example 2.

When the concentration of dipping process solution is more than 0.04, no static marks appear.

EXAMPLE 3 After 5 ml of a 4 percent aqueous solution-of saponin as a wetting agent was added to 1 kg of a high speed light sensitive photographic emulsion containing6 percent gelatin and 12 percentsilver iodobromide, this best,

B: good,

C: bad, and D: worst.

As is seen in Table 4, the use of the antistatic agent of the present invention leads to no static marks, and thedegree of antistatic i ty is ver y h igh. In addition, the states of the coating layer are best, and the photographic characteristics are also good.

EXAMPLE 4 5 ml of a 4 percent aqueous solution of saponin were added to 1 kg of a negative photographic high sensitivity emulsion containing 7 percent gelatin and 8 percent silver iodobromide. The processed emulsion was applied to a cellulose triacetate support which was undercoated in advance, and then was cooled and set. Further, solutions of a surface protection layer, obtained by adding ml of a 1 percent aqueous solution of Antistatic Agent I or II of the present invention prepared as in the process of Example 1 to 1 kg of a 2 percent aqueous solution of gelatin, were applied on the support, and were dried after being cooled and set. The state of the applied surface was extremely uniform and in good condition without blur and repellence. After being left at 20 percent RH for enough time, the film was passed through a high speed camera (Mitchell) and was examined as to the state of static marks. The results are shown in Table 5.

TABLE 5 Antistatic Agen Static Marks Examined by Camera Test I II No Antistatic Agent no appearance of static marks solution of gelatin, were added to the processed solution, cooled and set, and then dried. The respective surface layer was a uniformfilm with nearly no blurs and no repellences. As a controlsample, a photographic film was prepared in the same way as in Example 1, by applying a surface protection layer containing 50 ml of a 4 percent aqueous solution of saponin to the film. The degree of antistaticity and the quantity of electric charge of the tilm'were examined in the same way as TABLE4 Quantity of State of Static Electric Charg Coating Antistatic Agent Marks (V) Layer 1 A 14 II A l8 A Saponin D 16 B No Antistatic Agent E 20 D EXAMPLES 10 ml of a 5 percent aqueous solution of Compound 9 shown above were added to l kg of a high speed lightsensitive photographic emulsion containing 6 percent gelatin and 12 percent silver iodobromide. An applying solution for a surface protection layer was also prepared by adding 50 ml of a 5 percent aqueous solution NOTE: The method of estimating the degree of static marks was the same as in Example 1.

The estimation of the state of the coating layer was the same as in Example 3.

EXAMPLE 6 A light-sensitive emulsion obtained by successive application of a high speed light-sensitive photographic emulsion containing a color coupler and an aqueous solution of gelatin without an antistatic agent as a surface protection layer was treated by a soaking processing in the aqueous solution of antistatic agent of the present invention prepared in the same way as in Example l. The photographic film samples processed by soaking respectively were left at 40 percent RH for enough time after drying. Then, the samples were passed between two rollers and led into a Faraday Gauge. The quantity of electric charge generated on the samples was measured by a vacuum voltmeter. F urther, a white rubber sheet was put on the surface of the photographic film sample. After being subjected to reg ular friction by rolling on the white rubber sheet under the conditions of 23C and 40 percent Rl-l, the white rubber sheet was removed. The obtained film was developed, and the degree of aritistaticity was estimated by the quantity of built-up static marks.

TABLE 7 Concentration of Quantity of Antistatic Aqueous Solution Electric Agent (wt. Static Marks Charge (V) l 0.2 g A 8 l 0.0! A 5 II 0.2 A 7 ll 0.01 A 5 III 0.2 A 3 Ill B 3 None E 25 said cationic surface active agent being selected from the group consisting of: N-octadecyl-N,N,N- tris(2-hydroxyethyl)ammonium chloride, N- octadecyl-N,N,N-tris(2-hydroxyethyl)ammonium bromide, N-tetradecyl-N,N,N-(2-hydroxyethyl- )ammonium chloride, N-octadecyl-N,N,N- trimethylammonium chloride, N-tetradecyl-N,N- 'dimethyl-N-benzyl-ammonium chloride, 3- dodecyloxy-2-hydroxypropyl-trimethylammonium bromide, 3-p-nonylphenyl-2-hydroxypropyl-tris(2- hydroxyethyl)ammonitim chloride, or 3- tetradecyloxy(2-hydroxypropyl)pyridinium chloride, whereby an antistatic effect is obtained without being accompanied by adverse influences on the photographic properties of said photographic material. 2. The light-sensitive photographic material as claimed in claim 1, wherein said anionic polymer and surface active agent are incorporated into different silver halide emulsion layers.

3. The light-sensitive photographic material as claimed in claim 1, wherein said anionic polymer is polyacrylic acid, polymethacrylic acid, maleic anhydride-isobutylene copolymer or maleic anhydridevinylbutyl ether copolymer.

4. The light-sensitive photographic material as claimed in claim 3, wherein the said anionic polymer is selected from the group consisting of sodium alginate and a polymer having repeating units of the following formulas:

OONa

wherein R is an alkyl group having one to four carbon K The"ligiiisaa itiva"55515555156 Gazer a1 as claimed in claim 1, wherein said betaine-type amphoteric surface active agent is N-octadecyl-N,N-dimethyla-carboxylic acid betaine, N-tetradecyl-N,N-(2- hydroxyethyl)-acarboxylic acid betaine, 2-dodecyl-N- (2-hydroxyethyl)imidazolium-d-carbortylic acid betaine, N-dodecyloxy-methyl-N,N-diethyl-a-carboxylic acid betaine, N-tetradecyi-N,N-di(poly-oxyethylene)- a-carboxylic acid betaine, or N-3-dodecylaminopropyl- N,N-dimethyl-a-carboxylic acid betaine.

6. The light-sensitive photographic material as claimed in claim 1, wherein the weight ratio of the surface active agent to the anionic polymer is 1/100 to l.

7. A light-sensitive photographic material comprising a support having coated thereon one or more silver halide emulsion layers and at least one subsidiary layer, at least one of said layers having therein or thereon an antistatic composition consisting essentially of A. an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof having at most only a slight antistatic effect, and

B. at least one of a cationic surface active agent and a betaine-type amphoteric surface active agent, 7 said cationic surface active agent being selected from the group consisting of: N-octadecyl-N,N,N- tris(2-hydroxyethyl)ammonium chloride, N- octadecyl-N,N,N -tris(2-hydroxyethyl)ammonium bromide, N-tetradecyl-N,N,N-(Z-hydroxyethyl- )ammonium chloride, N-octadecyl-N,N,N- trimethylammonium chloride, vN-tetradecyl-N,N- dimethyl-N-benzyl-ammonium chloride, '3- dodecyloxy-2-hydroxypropyl-trimethylammonium bromide,v 3-p-nonylphnyl-Z-hydroxypropyl-tris( 2- hydroxyethyl)ammonium chloride, or tetradecyloxy( 2-hydroxypropyl )pyridinium chloride,

5 whereby an antistatic effect is obtained without being accompanied by adverse influences on the photographic properties of said photographic material.

8. The light-sensitive photographic material as claimed in claim 7, wherein said anionic polymer and surface active agent are incorporated in different layers.

9. The light-sensitive photographic material as claimed in claim 7, wherein said anionic polymer is polyacrylic acid, polymethacrylic acid maleic anhyl5 dride-isobutylene copolymer ormaleic anhydridevinyl-butyl ether copolymer.

10. The light-sensitive photographic material as claimed in claim 9, wherein said anionic polymer is selected from the group consisting of sodium alginate and a polymer having repeating units of the following formulas:

7'51? o -o c \lH lH/\H2N/| Nat (5N9.

v OHa CH-CH CH 11- N8 Na CH3 43H: oH-c ano F9 o= $=o H 3 CHCH on CH \l L 0= =0 l H2 NaO ONE A 45 H CH3 CH3 crr,-o1r om-0H OONa I orn-oH om-o 11 COCHzCHaCOONB- I OOH O OH and

CHr-CH ONHCHzCOOH 11. The light-sensitive photographic material as claimed in claim 7, wherein said betaine-type amphoteric surface active agent is N-octadecyl-N,N-dimethyla-carboxylic acid betaine, N-tetradecyl-N,N-(2- hydroxyethyl)-a-carboxylic acid betaine, N- tetradecyloxy-(2-hydroxypropyl)-N,N-di(2- hydroxyethyl)-a-carboxylic acid betaine, 2-dodecyl-N- (2-hydr0xyethyl)imidazolium-a-carboxylic acid betaine, N-dodecyloxymethyl-N,N-diethyl-a-carboxylic acid betaine, N-tetradecyl-N,N-di(polyoxyethylene)-acarboxylic acid betaine, or N-3-dodecylamino-propyl- N,N-dimethyl-a-carboxylic acid betaine.

12. The light-sensitive photographic material as claimed in claim 7, wherein the weight ratio of the surface active agent to the anionic polymer is 1/100 to l.

13. The light-sensitive photographic material as claimed in claim 8, wherein said different coating layer is a subsidiary layer, a protective layer, an overcoat layer, a filter layer, an intermediate layer, or an antihalation layer. 

2. The light-sensitive photographic material as claimed in claim 1, wherein said anionic polymer and surface active agent are incorporated into different silver halide emulsion layers.
 3. The light-sensitive photographic material as claimed in claim 1, wherein said anionic polymer is polyacrylic acid, polymethacrylic acid, maleic anhydride-isobutylene copolymer or maleic anhydride-vinylbutyl ether copolymer.
 4. The light-sensitive photographic material as claimed in claim 3, wherein the said anionic polymer is selected from the group consisting of sodium alginate and a polymer having repeating units of the following formulas:
 5. The light-sensitive photographic material as claimed in claim 1, wherein said betaine-type amphoteric surface active agent is N-octadecyl-N,N-dimethyl- Alpha -carboxylic acid betaine, N-tetradecyl-N,N-(2-hydroxyethyl)- Alpha -carboxylic acid betaine, N-tetradecyloxy-(2-hydroxy-propyl)-N,N-di(2-hydroxyethyl)- Alpha -carboxylic acid betaine, 2-dodecyl-N-(2-hydroxyethyl)imidazolium- Alpha -carboxylic acid betaine, N-dodecyloxy-methyl-N,N-diethyl- Alpha -carboxylic acid betaine, N-tetradecyl-N,N-di(poly-oxyethylene)- Alpha -carboxylic acid betaine, or N-3-dodecylaminopropyl-N,N-dimethyl- Alpha -carboxylic acid betaine.
 6. The light-sensitiVe photographic material as claimed in claim 1, wherein the weight ratio of the surface active agent to the anionic polymer is 1/100 to
 1. 7. A light-sensitive photographic material comprising a support having coated thereon one or more silver halide emulsion layers and at least one subsidiary layer, at least one of said layers having therein or thereon an antistatic composition consisting essentially of A. an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof having at most only a slight antistatic effect, and B. at least one of a cationic surface active agent and a betaine-type amphoteric surface active agent, said cationic surface active agent being selected from the group consisting of: N-octadecyl-N,N,N-tris(2-hydroxyethyl)ammonium chloride, N-octadecyl-N,N,N-tris(2-hydroxyethyl)ammonium bromide, N-tetradecyl-N,N,N-(2-hydroxyethyl)ammonium chloride, N-octadecyl-N,N,N-trimethylammonium chloride, N-tetradecyl-N,N-dimethyl-N-benzyl-ammonium chloride, 3-dodecyloxy-2-hydroxypropyl-trimethylammonium bromide, 3-p-nonylphenyl-2-hydroxypropyl-tris(2-hydroxyethyl)ammonium chloride, or 3-tetradecyloxy(2-hydroxypropyl)pyridinium chloride, whereby an antistatic effect is obtained without being accompanied by adverse influences on the photographic properties of said photographic material.
 8. The light-sensitive photographic material as claimed in claim 7, wherein said anionic polymer and surface active agent are incorporated in different layers.
 9. The light-sensitive photographic material as claimed in claim 7, wherein said anionic polymer is polyacrylic acid, polymethacrylic acid, maleic anhydride-isobutylene copolymer or maleic anhydride-vinyl-butyl ether copolymer.
 10. The light-sensitive photographic material as claimed in claim 9, wherein said anionic polymer is selected from the group consisting of sodium alginate and a polymer having repeating units of the following formulas:
 11. The light-sensitive photographic material as claimed in claim 7, wherein said betaine-type amphoteric surface active agent is N-octadecyl-N,N-dimethyl- Alpha -carboxylic acid betaine, N-tetradecyl-N,N-(2-hydroxyethyl)- Alpha -carboxylic acid betaine, N-tetradecyloxy-(2-hydroxypropyl)-N,N-di(2-hydroxyethyl)- Alpha -carboxylic acid betaine, 2-dodecyl-N-(2-hydroxyethyl)imidazolium- Alpha -carboxylic acid betaine, N-dodecyloxymethyl-N,N-diethyl- Alpha -carboxylic acid betaine, N-tetradecyl-N,N-di(polyoxyethylene)- Alpha -carboxylic acid betaine, or N-3-dodecylamino-propyl-N,N-dimethyl- Alpha -carboxylic acid betaine.
 12. The light-sensitive photographic material as claimed in claim 7, wherein the weight ratio of the surface active agent to the anionic polymer is 1/100 to
 1. 13. The light-sensitive photographic material as claimed in claim 8, wherein said different coating layer is a subsidiary layer, a protective layer, an overcoat layer, a filter layer, an intermediate layer, or an antihalation layer. 